Hydroperoxyisopropylphenyl carbonates

ABSTRACT

Isopropylphenyl esters are converted to di- or trihydric phenols via a novel autoxidation of the esters at high conversion rates to the corresponding hydroperoxyisopropylphenyl esters in the presence of a catalyst combination comprising at least two members selected from the group consisting of (i) a metal phthalocyanine; (ii) a di-tertiary alkyl peroxide; and (iii) a tertiary alkyl hydroperoxide. 
     Rearrangement of the hydroperoxyisopropylphenyl esters to the corresponding hydroxyphenyl esters and the hydrolysis of the latter compounds provides the phenols in overall yields (from the starting esters) heretofore not obtainable. Novel bis(hydroperoxyisopropylphenyl)carbonates are described which are attractive intermediates for the intermediate bisphenol carbonate or the final hydroquinone hydrolysis product.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a division of copending application Ser. No. 879,788U.S. Pat. No. 4,164,510 filed Feb. 21, 1978 which in turn is acontinuation-in-part of copending application, Ser. No. 818,233 filedJuly 22, 1977, abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to the autoxidation of alkyl aromatic compoundsand is more particularly concerned with an improved process for thepreparation of hydroperoxyisopropylphenyl esters, including novelbis(hydroperoxyisopropylphenyl)carbonates andbis(hydroxyphenyl)carbonates produced therefrom, and further relates toan improved process for the preparation of di- and trihydric phenols viasaid hydroperoxyisopropylphenyl esters.

2. Description of the Prior Art

The autoxidation of cumene and cumene type hydrocarbons to cumenehydroperoxide and the like is a well known procedure; see, for example,U.S. Pat. Nos. 2,820,064, 2,954,405, 3,634,328, and 3,803,243. U.S. Pat.No. 3,666,815 discloses similar type oxidation procedures leading toalcohol products and U.S. Pat. No. 3,816,548 shows the catalyticoxidation of isoparaffin hydrocarbons to alcohols using techniquessimilar to those described for the aromatic compounds.

Kropf et al (Liebigs Ann. Chem. 1975, 2010-2022 and J. Prakt Chem. 9,173-86, 1959) have disclosed the use of metal phthalocyanines ascatalysts in oxidizing cumene type hydrocarbons to cumyl hydroperoxides.

When an oxygen substituent, as in the case of an isopropylphenyl ester,is attached to the aromatic ring the autoxidation of the isopropyl groupto the α-cumyl hydroperoxide derivative is complicated by the formationof side products and yields or conversions tend to be lower. Generallyspeaking, this is attributed to the presence of trace amounts ofphenolic impurities which can arise from the hydrolysis of the phenylester.

Hydroperoxides of difficultly saponifiable esters of isopropylphenolsare prepared in the liquid state with an oxygen containing gas at atemperature of about 20° C. to about 125° C. in the presence of anantacid as shown in U.S. Pat. No. 2,799,695. Reaction times are verylong, of the order of days, while conversions are low.

U.S. Pat. No. 2,799,698 discloses the oxidation of p-isopropylphenylacetate directly to hydroquinone diacetate in the presence of aceticanhydride.

The autoxidation of difficultly hydrolyzable esters ofα,α-dialkylmethylphenols is reported in U.S. Pat. No. 2,799,715 bycontacting said esters with an oxygen gas at 20° C. to 125° C. in thepresence of an antacid. The hydroperoxides so formed are converted tothe corresponding dihydric phenols. As in the case of U.S. Pat. No.2,799,695, the reaction times are very long with low conversions.

Zimmer (U.S. Pat. No. 3,028,410) discloses the autoxidation of variousisopropylphenyl esters to hydroperoxide derivatives. Reaction conditionsinclude high reaction temperatures of 140° C. to 160° C. which isconsidered to be a high range when working with organic peroxidicmaterials; mono or dhydroperoxides of isopropylaromatic compounds aredisclosed as catalysts. Conversions are reported on the basis of totalhydroperoxide content of the reaction mixture alone. U.S. Pat. No.2,954,405 broadly discloses the use of combinations of metalphthalocyanines with hydroperoxides in the autoxidation of alkylaromatic compounds.

The hydroperoxyisopropylphenyl esters disclosed in the art cited aboveserve as intermediates for the preparation of dihydric phenols by theacid catalyzed rearrangement of the hydroperoxyisopropyl compounds tothe corresponding hydroxyphenyl esters and acetone and subsequentsaponification of the hydroxyphenyl ester to the dihydric phenol; seeU.S. Pat. Nos. 2,799,695, 2,799,715, and 3,028,410.

It has now been discovered that isopropylphenyl esters can beautoxidized with essentially no induction period at a much faster ratewith a higher conversion and selectivity and higher isolated yield ofdesired hydroperoxide product than has hitherto been possible whileoperating at relatively low and safe temperatures. Furthermore, the morefacile preparation of the hydroperoxyisopropylphenyl esters provides foran improved means for the preparation of di- or trihydric phenols inoverall increased yields.

SUMMARY OF THE INVENTION

This invention comprises a process for the autoxidation of anisopropylphenyl ester to the hydroperoxyisopropylphenyl ester in thepresence of oxygen wherein the improvement comprises carrying out saidautoxidation at a temperature of from about 80° C. to about 130° C. inthe presence of a catalyst combination comprising at least two membersof the group consisting of (i) a metal phthalocyanine; (ii) adi-tertiary alkyl peroxide; and (iii) a tertiary alkyl hydroperoxide.

The invention also comprises an improved process for the preparation ofdi- or trihydric phenols.

The invention also comprises certain novel hydroperoxyisopropyl phenylesters.

The term "isopropylphenyl ester" means a phenyl ester having the formula##STR1## wherein n equals 1 or 2 provided that when n equals 1 theisopropyl radical is substituted either in the meta or para position onthe phenyl ring relative to the ester group and when n equals 2 theisopropyl radicals are substituted in each meta position, and wherein Ris selected from the group consisting of alkyl from 1 to 8 carbon atoms,inclusive, aryl from 6 to 12 carbon atoms, inclusive, alkaryl from 7 to14 carbon atoms inclusive, aralkyl from 7 to 14 carbon atoms, inclusive,and radicals having the formula ##STR2## wherein n is defined as above,R₁ is selected from the group consisting of hydrogen and alkyl from 1 to4 carbon atoms, and the carbophenoxy substituent can be in the ortho,meta, or para position to the valency bond of the radical.

The term "hydroperoxyisopropylphenyl ester" means the autoxidationproduct derived from formula (I) wherein the tertiary isopropyl hydrogenatom has been replaced by the hydroperoxy radical and saidhydroperoxyisopropylphenyl ester has the formula ##STR3## wherein n andR are both defined as set forth above and further provided that when theradical R contains isopropyl radicals as in the case of Ia or Ib setforth above then said isopropyl radicals may also have their tertiaryisopropyl hydrogen atoms replaced by the hydroperoxy radical.

The term "alkyl from 1 to 4 carbon atoms" means methyl, ethyl, propyl,butyl, and isomeric forms thereof.

The term "alkyl from 1 to 8 carbon atoms" means the alkyl groups setforth above as well as pentyl, hexyl, heptyl, octyl, and isomeric formsthereof.

The term "aryl from 6 to 12 carbon atoms" means phenyl, biphenyl,naphthyl, and the like.

The term "alkaryl from 7 to 14 carbon atoms" means tolyl, ethylphenyl,xylyl, 3,5-dimethyl-α-naphthyl, 3,5-diethyl-α-naphthyl, and the like.

The term "aralkyl from 7 to 14 carbon atoms" means benzyl,p-methylbenzyl, p-ethylbenzyl, β-phenylethyl, γ-phenylpropyl,δ-phenylbutyl, δ-(2,4-dimethylphenyl)butyl, δ-(2,4-diethylphenyl)butyl,and the like.

The term "tertiary alkyl hydroperoxide" means a hydroperoxide compoundcontaining at least one hydroperoxide group wherein the oxygen is bondedto a tertiary carbon atom wherein at least two of the other groupsbonded to said carbon atom are alkyl from 1 to 8 carbon atoms and thethird group bonded to said carbon is selected from the class consistingof alkyl from 1 to 8 carbon atoms, cycloalkyl from 5 to 10 carbon atomsinclusive, and aryl from 6 to 12 carbon atoms inclusive. Illustrative ofsaid tertiary alkyl hydroperoxides are t-butyl hydroperoxide,1,1,3,3-tetramethylbutyl hydroperoxide,2,5-dihydroperoxy-2,5-dimethylhexane, p-menthane hydroperoxide, cumenehydroperoxide, and 1,4-di(hydroperoxyisopropyl)benzene, and the like.

The term "di-tertiary alkyl peroxide" means a peroxidic compoundcontaining at least one peroxy grouping wherein each oxygen atom isbonded to a tertiary carbon atom wherein the remaining groups attachedto said carbon atom are the same as defined above. Illustrative of saiddi-tertiary alkyl peroxides are di-t-butyl peroxide, dicumyl peroxide,2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and the like.

DETAILED DESCRIPTION OF THE INVENTION

The process of the present invention can be used for the preparation ofdi- or trihydric phenols in accordance with the following reactionscheme. ##STR4##

The isopropylphenyl ester (I) defined hereinabove is autoxidized by thenovel process in accordance with the present invention to thehydroperoxyisopropylphenyl ester (II) also defined hereinabove. Acidcatalyzed rearrangement of (II) gives rise to the formation of acetoneand the formation of a phenolic hydroxyl function at the site originallyoccupied by the hydroperoxyisopropyl group to form (III). Simple acid orbase catalyzed hydrolysis of the ester group of (III) gives rise to theformation of another phenolic hydroxyl group as illustrated in (IV).

The principal polyhydric phenols prepared in accordance with the presentinvention are those di- or trihydric phenols having the structure (IV).However, it will be obvious to one skilled in the art that other phenolshaving the formula (III) can also be prepared in accordance with thepresent invention wherein the ester group is left intact. The hydroxylfunctionality of (III) will depend on the value of n and the nature ofthe radical R as defined hereinbefore, and can have a value from one tofour inclusive.

A preferred isopropylphenyl ester to be used in accordance with thepresent invention has the formula (I) wherein n is defined as above andR is selected from the group consisting of alkyl, aryl, and the radical(Ia) all defined as above.

A most preferred isopropylphenyl ester has the formula ##STR5## whereinR is selected from the group consisting of alkyl, aryl, and the radical(Ia) wherein n=1 and the isopropyl group is in the para position, andalkyl and aryl are as defined above.

The improved process in accordance with the present invention for theautoxidation of an isopropylphenyl ester (I) to thehydroperoxyisopropylphenyl ester (II) is carried out conveniently byintimately mixing the isopropylphenyl ester with a moisture free gasrich in oxygen content, such as air, but, preferably oxygen, at atemperature of from about 80° C. to about 130° C., preferably from about100° C. to about 120° C., in the presence of one of the catalystcombinations set forth above. The individual components (i), (ii), and(iii) can be paired in any order desired just so long as at least twoare present in the combination during the autoxidation.

The progress of the autoxidation reaction can be studied using anyconvenient analytical technique. However, a particularly simple, rapid,yet accurate method comprises removing aliquots periodically from thereaction mixture and determining the proton nuclear magnetic resonancespectrum of the sample. A comparison of the integration area of protonresonance arising from the methyl groups of the hydroperoxyisopropylgroup with the integration area of proton resonance derived from themethyl groups of the starting isopropyl group provides a rapid measureof the total mole percent conversion to hydroperoxide. From this data arate of mole percent conversion can be determined.

While the autoxidation process in accordance with the present inventioncan be run to high molar percent conversions, for example in excess of40 mole percent, it is preferred that the conversion not be allowed toexceed about 40 mole percent so that hydroperoxide product selectivitycan be maximized to well above 90 percent. Otherwise, increasedconversion leads to poorer selectivity. The starting material orincompletely oxidized material is simply recovered and recycled insubsequent autoxidations.

Yet another convenient means for analyzing the progress of the reaction,and, more particularly, the actual product selectivity or percentageconcentration of each product formed which includes the side-products aswell as the compound (II), is to analyze an aliquot by high pressureliquid chromatography (HPLC) (see Modern Practice of LiquidChromatography edited by J. J. Kirkland, 1971, Wiley Intersciences, Div.of John Wiley & Sons, Inc., New York, N.Y.).

Using these analytical procedures in studying the autoxidation processof the present invention, rates of conversion have been observed (up to40 mole percent in 3 hours) at levels of product selectivity (greaterthan 90 percent) which hitherto have not been obtainable with prior artmethods.

Moreover, these analytical methods provide a simple means fordetermining when the autoxidation may be conveniently stopped. Generallyspeaking, the autoxidation is conducted over a period of time from about1 hour to about 15 hours and preferably from about 2 hours to about 8hours.

The t-alkyl hydroperoxide and di-t-alkyl peroxide components, whetheremployed together or separately, are each advantageously employed in thecatalyst combination in an amount of from about 0.1 percent by weight toabout 4 percent by weight of (I) and preferably from about 0.3 to about2.0 percent.

The use of peroxy ester compounds such as dibenzoyl peroxide, stearoylperoxide, and the like are specifically excluded because the use of suchcompounds is deleterious due to the trace amounts of acidic impuritieswhich cause trace hydrolysis to occur at the phenyl ester groups. Thisin turn is highly detrimental to the autoxidation.

Although not essential, the autoxidation can be carried out under aslight positive pressure of oxygen. The oxygen containing gas can beintroduced into the reaction mixture using any suitable means known tothose skilled in the art for the distribution and admixture of a gasinto a liquid system. Illustratively, the gas can be sparged through adip tube fitted with a fritted disc or other dispersing means known tothose skilled in the art.

The metal phthalocyanine component of the catalyst combination that canbe employed in the present invention is selected from the groupconsisting of copper, zinc, palladium, platinum, silver, and mercury. Aparticularly preferred phthalocyanine is copper phthalocyanine. Themetal phthalocyanines are easily prepared using known techniques; seefor example U.S. Pat. No. 2,954,405 (col. 3 lines 53-67) or else theyare commercially available.

The metal phthalocyanine is advantageously employed in an amount of fromabout 0.001 percent by weight to about 1.0 percent by weight of theisopropylphenyl ester (I) and preferably from about 0.01 to about 0.6percent.

Bulk autoxidation or autoxidation in a solvent diluent can be carriedout in accordance with the present invention. Generally speaking, thestarting material (I), if not a liquid at room temperature, is liquefiedwhen exposed to the temperature ranges set forth above for carrying outthe reaction.

In a preferred embodiment of the present invention the autoxidation isconducted in the presence of an inert aromatic solvent. The use ofsolvent reduces the occurrence of radical termination steps therebyincreasing conversion rates. Accordingly, the quantity of solventemployed is not critical and can, conveniently, vary from about 20percent by weight to about 200 percent by weight of the isopropylphenylester (I).

Any suitable inert aromatic solvent can be employed. A preferred groupof solvents comprises benzene, t-butylbenzene, the halogenated benzenessuch as chlorobenzene, o-dichlorobenzene, and the like. A particularlypreferred solvent is chlorobenzene.

Particularly preferred combinations of catalyst and solvent inaccordance with the present invention are (1) t-butyl hydroperoxide,copper phthalocyanine and chlorobenzene; and (2) t-butyl hydroperoxide,dicumyl peroxide and chlorobenzene.

The isopropylphenyl esters (I) employed in the present process aredefined hereinbefore and specifically excluded are those esters whereinthe isopropyl group is substituted on the position ortho to the estergroup. Illustrative examples of the isopropylphenyl esters used in thepresent process are p-(or meta)isopropylphenyl acetate, p-(ormeta)isopropylphenyl propionate, p-(or meta)isopropylphenyl butyrate,p-(or meta)isopropylphenyl valerate, p-(or meta)isopropylphenylcaproate, p-(or meta)isopropylphenyl heptylate, p-(ormeta)isopropylphenyl caprylate, and the like; p-(or meta)isopropylphenylbenzoate, p-(or meta)isopropylphenyl naphthoate, p-(ormeta)isopropylphenyl-p-toluate, p-(ormeta)isopropylphenyl-p-ethylbenzoate, p-(ormeta)isopropylphenyl-3,5-dimethyl-α-naphthoate, p-(ormeta)isopropylphenyl-α-phenylacetate, p-(ormeta)isopropylphenyl-β-phenylpropionate, and the like; illustrativeexamples of the esters (I) wherein n is 2 are 3,5-diisopropylphenylacetate, 3,5-diisopropylphenyl benzoate,3,5-diisopropylphenyl-p-toluate, 3,5-diisopropylphenyl-α-phenylacetate,and the like; bis(p-isopropylphenyl)terephthalate,bis(m-isopropylphenyl)terephthalate,bis(p-isopropylphenyl)2-methylterephthalate,bis(p-isopropylphenyl)isophthalate, bis(p-isopropylphenyl)phthalate, andthe like; bis(p-isopropylphenyl)carbonate,bis(m-isopropylphenyl)carbonate, bis(3,5-diisopropylphenyl)carbonate,and the like.

A preferred group of esters (I) is comprised of p-isopropylphenylacetate, p-isopropylphenyl benzoate, bis(p-isopropylphenyl)carbonate,bis(m-isopropylphenyl)carbonte, bis(3,5-diisopropylphenyl)carbonate, and3,5-diisopropyl-phenyl benzoate.

The carbonate esters are easily prepared using methods well known tothose skilled in the art by the reaction of an excess of the appropriateisopropylphenol with phosgene, preferably in the ratio of 2:1respectively, in the presence of a base to absorb the hydrogen chlorideformed during the reaction; see for example, Synthetic Organic Chemistryby R. B. Wagner and H. D. Zook, page 483, 1953, John Wiley and Sons, NewYork, N.Y.

In an unexpected advantage to flow from the process of the presentinvention, the use of the bis(isopropylphenyl)carbonate compounds asstarting materials provides a highly efficient and economic route tophenols in high purity, particularly hydroquinone. The use of thereadily available and economically priced phosgene as the ester formingcomponent with an isopropylphenol to form thesebis(isopropylphenyl)carbonate starting materials is a novel andsurprisingly advantageous technique.

The acid catalyzed rearrangement of hydroperoxyisopropylphenol esters(II) to yield acetone and the corresponding hydroxyphenyl ester (III)with subsequent hydrolysis of the latter to the phenol (IV) are wellknown procedures in the art; see for example U.S. Pat. Nos. 2,799,695,2,799,698, 2,799,715, and 3,028,410 cited supra whose disclosures inthis respect are herein incorporated by reference.

The rearrangement of the hydroperoxide (II) to the phenolic compound(III) can be carried out on the reaction mixture as it is obtaineddirectly from the autoxidation step. The presence or absence of solventis not a critical feature. While the hydroperoxide can be isolated, and,even purified if desired, it is not essential to the overall efficiencyof the rearrangement and subsequent hydrolysis to the phenol. In apreferred embodiment, the hydroperoxide (II) is not isolated butrearranged in the reaction mixture in the presence of solvent.

Optionally, the relatively large proportion of starting isopropylphenylester (I), if easily distillable, can be removed from the crudeautoxidation mixture prior to the rearrangement step. However, this isnot essential as the isopropylphenyl esters (I) used in the presentprocess are completely stable to the room temperature basicsaponification conditions used to hydrolyze the ester grouping of thecompounds (III), and, consequently, unreacted (I) can be recovered atthe very end of the process after (IV) has been formed. A noteworthycharacteristic of the hydroxyphenyl esters (III) is the ease with whichthe ester grouping can be hydrolyzed once the hydroxyl group is presenton the aromatic ring. This will be discussed in detail hereinbelow. Theprecursor isopropylphenyl ester is not characterized by this same easeof hydrolyzability.

As noted above, the rearrangement of (II) is an acid catalyzed reactionand well known in the art and any of the methods described in thereferences cited supra can be employed in the present process. The acidcatalyzed rearrangement is advantageously carried out within atemperature range of from about 0° C. to about 100° C., and preferablyfrom about 20° C. to about 80° C. The time for the rearrangement tooccur is not a critical feature and will vary depending on such factorsas temperature, presence or absence of solvent, scale of reaction, etc.Generally speaking, the time will vary from a matter of minutes (about15 minutes) to a number of hours (about 4 hours).

Acid catalysts such as sulfuric, hydrochloric or p-toluenesulfonicacids, boron trifluoride etherate, or the like are used, advantageouslyin an amount of from about 0.01 weight percent to about 5.0 weightpercent of compound (II) and preferably from about 0.1 weight percent toabout 1.0 weight percent. A preferred group comprises boron trifluorideetherate and sulfuric acid. A most preferred catalyst is borontrifluoride etherate.

The rearrangement can proceed in high yield (>95%) to acetone and thehydroxyphenyl ester compound (III). The impurities present are veryminor amounts of the acetophenone derivative, which arises from therearrangement of (II), and an isopropenylphenyl ester. The formerimpurity is formed in the autoxidation step while the latter arises fromthe dehydration, during the rearrangement, of the hydroxyisopropylphenylester side product which is also formed in the autoxidation step as aminor impurity.

The bisphenol carbonates of formula (III) wherein R is thehydroxyphenyloxy radical [derived from (Ia)], find particular utility inthe preparation of polycarbonate polymers well known to those skilled inthe art.

When it becomes desirable to isolate the hydroxyphenyl esters (III)formed from the rearrangement, as in the case of the bisphenolcarbonates referred to hereinabove, a non-solvent for the hydroxyphenylester is simply added to the crude reaction mixture. For example, theaddition of solvents such as hexane, petroleum ether, benzene, methylenechloride, and the like will cause the selective precipitation of thedihydroxyphenyl ester from any monohydroxyl compound and particularlythe bisphenol carbonates as crystalline solids.

The hydrolysis of the hydroxyphenyl esters (III) to the correspondingphenols (IV) is readily accomplished using either acid or base catalyzedhydrolysis. However, base catalyzed hydrolysis is preferred and any ofthe techniques set forth in the patents cited supra whose disclosureshave been incorporated herein can be used in the present process.

A preferred method for the hydrolysis of the crude rearrangement mixturecomprises simply shaking the reaction solution with dilute aqueousalkali metal hydroxide solution (e.g. 5-20 wt. percent sodium hydroxidesolution) at room temperature. Preferably, the hydrolysis is carried outunder nitrogen, or else, in the presence of a minor amount of anantioxidant such as sodium sulfite to inhibit possible oxidation of theformed phenols (IV) which are somewhat susceptible to air oxidation inbasic solution.

The phenols can be isolated using any convenient separation methodsknown to those skilled in the art. The alkali metal hydroxide is eitheracidified by dilute hydrochloric acid or neutralized by the addition ofcarbon dioxide, whereafter the product can be either extracted from thesolution or will crystallize therefrom.

The overall process according to the present invention provides in-handyields of phenols, and hydroquinone in particular, at conversion levelsand rates of conversion based on starting isopropylphenyl ester,heretofore not obtainable.

The new process offers high conversions in the autoxidation step at highselectivities (90-95%) which gives rise to overall yields of compoundslike hydroquinone as high, or higher, than 90%. Furthermore, thedihydric phenols, which are recognized in the art as being difficult toobtain in a high state of purity, are obtained from the present processin excellent purity.

The dihydric phenols produced in accordance with the present inventionsuch as hydroquinone, resorcinol, and the like are used as intermediatesin the preparation of other compositions, for example in the preparationof various polymers such as poly(1,4-phenylene adipate),poly(1,3-phenylene adipate), poly(1,4-phenylene phosphonate),poly(1,4-phenylene sebacate), and the like.

Hydroquinone is particularly useful in photographic developerformulations and also as an oxidation inhibitor.

The following examples describe the manner and process of making andusing the invention and set forth the best mode contemplated by theinventor of carrying out the invention but are not to be construed aslimiting.

ANALYTICAL METHODS

The analyses of the autoxidation reactions exemplified below and theproducts obtained therefrom were performed either by (A) the techniqueof high pressure liquid chromatography(HPLC) or (B) by the nuclearmagnetic resonance(NMR) measurements which methods are describedgenerally below. The latter technique was preferably used in monitoringthe progress of the autoxidation while the former was preferably used indetermining product identity and concentration.

(A) HPLC analysis was performed in a Waters Model 6000 Machine with dualdetectors (Model 202/R401), Waters Associates, Milford, Mass., 01757, bypassing an aliquot of the reaction solution through a μ-Porasil column(4mm ID×30 cm.length) operating at a flow rate of 1.2-1.5 ml./min. andusing a solvent mixture of acetonitrile 7.5% by volume and ethylenedichloride 92.5% by volume at room temperature.

(B) NMR analysis was performed in a Varian T-60 spectrometer usinginternal TMS as standard in carbon tetrachloride as solvent on analiquot of the reaction mixture by measuring the proton resonance. Thesinglet peak at δ 1.52 for the protons of the two methyl groups of thehydroperoxyisopropyl group was compared to the doublet resonance at δ1.23 for the methyl protons of the unreacted isopropyl group.

EXAMPLE 1

A three-necked round bottom flask equipped with an oxygen bubbler, athermometer fitted with a thermometer regulator, magnetic stirrer, and acondenser was charged with 93.06 g. (0.523 mole) of p-isopropylphenylacetate, 0.40 g. (0.43 wt. % based on the acetate) of copperphthalocyanine, and a trace amount (2 drops or about 0.1 g.) of t-butylperoxide. Oxygen was bubbled into the solution at a rapid rate (flowrate 25 ml./min.) while the solution was heated for 30 minutes at125°-130° C. and thereafter at 115° C. for 5 hours.

The progress of the autoxidation to p-hydroperoxyisopropylphenyl acetatewas monitored using the NMR technique described above and showed thefollowing progression of the conversion: at 60 minutes, 7.5%; at 120minutes, 18.8%; at 180 minutes, 23.5%; and at 300 minutes, 28.8%. Therate of conversion was 8 mole%/hour and there was no induction periodprior to the beginning of the autoxidation. HPLC analysis showed a 91%content (selectivity) in the oxidation product mixture ofp-hydroperoxyisopropylphenyl acetate.

EXAMPLE 2

A round bottomed flask equipped according to Example 1 was charged with10.2 g. (0.057 mole) of p-isopropylphenyl acetate, 0.10 g. (1.0 wt. %)of t-butyl hydroperoxide, 0.02 g. (0.2 wt. %) of copper phthalocyanine(supplied by Eastman Chemicals, Rochester, New York), and 5.0 g. (49 wt.%) of chlorobenzene. Oxygen was bubbled into the stirred solution (flowrate 20 ml./min.) for a 10 minute period at a solution temperature of120°-125° C. and then for 4 hours at 115°±3° C. The conversion rate wasmonitored by the NMR technique and the actual content (selectivity) ofthe desired p-hydroperoxyisopropylphenyl acetate was concurrentlymeasured (where it is noted below) and the results are shown in thefollowing tabulation.

    ______________________________________                                                                   % Content of                                       Time of Reaction                                                                           Mole % Conversion                                                                           Desired                                            (minutes)    to Hydroperoxide                                                                            Hydroperoxide                                      ______________________________________                                         30           5.6          --                                                  60          11.1          --                                                  90          19.8          --                                                 120          26.7          93.4                                               150          37.6          91.8                                               180          43.2          89.8                                               210          46.5          --                                                 240          46.7          88.9                                               ______________________________________                                    

Based on the above mole % conversion, the actual rate of conversion was16 mole %/hour with little or no induction period.

EXAMPLE 3

A round bottomed flask equipped according to Example 1 was charged with34.45 g. (0.144 mole) of p-isopropylphenyl benzoate, 0.17 g. (0.49 wt.%) of di-t-butyl peroxide, 0.20 g. (0.58 wt. %) copper phthalocyanine,and 10 ml. of benzene. Oxygen was bubbled into the solution (flow rate20 ml./min.) for about 20 minutes at a solution temperature of 120°-125°C. and thereafter for 10 hours at 115° C.±2° C. The progress of theautoxidation was followed by NMR analysis to determine the conversion ofthe starting benzoate to the desired p-hydroperoxyisopropylphenylbenzoate. After 180 minutes the molar conversion was 11.3%; 300 minutes,21.0%; 480 minutes, 27.7%; finally at 600 minutes, 36.6%. The rate ofconversion was 4.4 mole %/hour and the selectivity of the desiredproduct determined by HPLC was 87.4%. The autoxidation initiated withoutan induction period.

The reaction solution was diluted with 100 ml. of benzene and filteredto recover the copper phthalocyanine, wt., 0.21 g. To the filtrate therewere added 6 drops of boron trifluoride etherate and this solutionstirred for 4 hours. The temperature was initially room temperature(circa 20° C.) but increased to 60° C. and returned to room temperatureover the 4 hour period. A precipitate of p-hydroxyphenyl benzoate wascollected, wt., 4.89 g., m.p. 158°-161° C. To the mother liquor, 100 ml.of carbon tetrachloride was added causing the precipitation ofadditional p-hydroxyphenyl benzoate, wt., 5.66 g., m.p. 156°-162° C. Thetotal yield of 10.55 g. of p-hydroxyphenyl benzoate was equivalent to a93.4% yield.

EXAMPLE 4

A round bottomed flask equipped according to Example 1 was charged with15.0 g. (0.0625 mole) of p-isopropylphenyl benzoate, 0.15 g. (1.0 wt. %)of t-butyl hydroperoxide, 0.03 g. (0.2 wt. %) of copper phthalocyanine,and 3.0 g. (20 wt. %) of chlorobenzene. Oxygen was bubbled into thesolution (flow rate 20 ml./min.) for 5 minutes at a solution temperatureof 125°-130° C. and thereafter for 4 hours at 115°±3° C. The progress ofthe autoxidation was followed by NMR analysis to determine theconversion of the starting material to p-hydroperoxyisopropylphenylbenzoate. After 30 minutes the molar conversion was 2.1%; 60 minutes,9.6%; 120 minutes, 20.5%; 180 minutes, 28.5%; finally at 240 minutes,39.4%. The rate of conversion was 9.8 mole %/hour and the selectivity ofthe desired product determined by HPLC was 94.5%. There was no inductionperiod.

EXAMPLE 5

p-Isopropylphenol (200.5 g., 1.474 moles) was dissolved with 1.5 litersof 2.2 N sodium hydroxide solution. This solution was charged to a 3liter three-necked round bottom flask equipped with a mechanical stirrerand an addition funnel. Triethylamine (2.0 g.) was added to the solutionwhile it was cooled to 0° C. by means of an ice bath. To the solutionthere was added over a 2 hour period, a solution of 150 g. (1.52 moles)of phosgene in 200 ml. of toluene. The solution was then allowed to warmup to room temperature by continued stirring for 2 hours.

The reaction solution was extracted with 3×130 ml. portions of ether andthe combined ether fractions dried over magnesium sulfate. Ether andvolatile material was removed in vacuo to provide 223 g. (approximately100% yield) of di(p-cumyl)carbonate or bis(p-isopropylphenyl) carbonate.It was recrystallized twice from 300 ml. of methanol each time andyielded 205.1 g. (93.4%) of needles of pure di(p-cumyl)carbonate whichhas the following properties: m.p. 59°-60° C.; infrared absorptionspectrum (CHCl₃) (cm⁻¹), 3040, 2970, 1755, 1605, 1508, 1460, 1420, 1385,1365, 1235, 1190, 1163, 1200, 1057, 1020, 1010, 889, and 829; NMR(CDCl₃)at δ 7.15 (s,8), 2.89 (m,2), 1.22 (d,12); HPLC retention time of 2.45minutes, μ-Porasil column (4 mm. ID×30 cm. length); solvent: 9.75%acetonitrile+90.25% ethylene dichloride; and the following elementalanalysis

Calcd. for C₁₉ H₂₂ O₃ : C, 76.48%; H, 7.43% Found: C, 76.37%; H, 7.47%.

The following process although not in accordance with the presentinvention was employed to obtaindi(p-hydroperoxyisopropylphenyl)carbonate.

A round bottomed flask equipped according to Example 1 was charged with46.10 g. (0.155 mole) of di(p-cumyl) carbonate, 0.25 g. (0.54 wt. %) ofdi-t-butyl peroxide and 6 ml. of benzene. Oxygen was bubbled into thesolution (flow rate about 15 ml./min.) for 15 minutes at a solutiontemperature of 120°-125° C. and thereafter for 7 hours at 115° C. NMRanalysis was used to observe the following molar hydroperoxideformation: after 120 minutes, 8.9%, 240 minutes, 18.6%; 360 minutes,26.1%; finally at 420 minutes, 29.6%. The rate of conversion was 4.5mole %/hour. HPLC analysis showed the following selectivity:di(p-hydroperoxyisopropylphenyl)carbonate, 11.8%;(p-hydroperoxyisopropylphenyl)cumyl carbonate, 85.0%;(p-hydroxyisopropylphenyl)cumyl carbonate, 3.2%.

Recrystallization of a sample of thedi(p-hydroperoxyisopropylphenyl)carbonate from p-dioxane providedcrystalline needles, m.p. 122°-124° C.; HPLC retention time of 4.79minutes (μ-Porasil column 4 mm. ID×30 cm. length, solvent 9.75%acetonitrile and 90.25% ethylene chloride), and having the followingelemental analysis

Calcd. for C₁₉ H₂₂ O₇ : C, 62.97%; H, 6.12% Found: C, 62.80%; H, 6.15%.

The following process was in accordance with the present invention anddemonstrates the much higher selectivity in comparison to the experimentabove.

A round bottom flask equipped according to Example 1 was charged with36.77 g. (0.123 mole) of di(p-cumyl) carbonate prepared above, 0.22 g.(0.58 wt. %) of copper phthalocyanine, 0.12 g. (0.33 wt. %) ofdi-t-butyl peroxide, and 10 ml. of benzene. Oxygen was bubbled into thesolution (flow rate of 40 ml./min.) for 20 minutes at a solutiontemperature of 125°-130° C. and thereafter for another eight hours and40 minutes. NMR and HPLC were used to monitor the progress of thereaction and NMR showed the following molar hydroperoxide formation:after 60 minutes, 3.8%; 120 minutes, 6.4%; 180 minutes, 11.7%; 300minutes, 22.8% 360 minutes, 26.1%; finally 540 minutes, 39.1%. The rateof conversion was 4.2 mole %/hour. HPLC showed the distribution of the 3major products to be mono-hydroperoxide (p-hydroperoxyisopropylphenylcumyl carbonate) 74.01%; mono-alcohol (p-hydroxyisopropylphenyl cumylcarbonate) 6.61 %; anddi-hydroperoxide[di(p-hydroperoxyisopropylphenyl)carbonate] 19.30%.There was no induction period.

The reaction mixture was diluted with 150 ml. of benzene and filtered torecover 0.21 g. (95.5% recovery) of copper phthalocyanine. The solutionwas stirred with 0.1 g. of boron trifluoride etherate over a period of2.25 hours during which time the solution was at 35°-60° C. from its ownexotherm. Evaporation of the benzene yielded 39.18 g. of crude solidproduct.

The solid residue was triturated with 200 ml. of hexane which uponevaporation afforded 14.10 g. of crystalline solid which contained about13 g. of starting di(p-cumyl)carbonate while the balance of 1.1 g.consisted of a 50/50 mixture of p-cumyl)p-isopropenylphenyl)carbonateand p-cumyl(p-hydroxyphenyl)carbonate.

The hexane insoluble solid portion of 19.50 g. consisted largely of themixture of p-cumyl(p-hydroxyphenyl)carbonate andbis(p-hydroxyphenyl)carbonate in the approximate ratio of 80%/20%respectively. The isolation of the latter bisphenol carbonate waseffected by triturating the solid with 2×50 ml. portions of methylenechloride. The undissolved portion, 6.6 g. (m.p. 150°-167° C.) wasrecrystallized from 20 ml. of 1,4-dioxane to yield 2.87 g. of needles ofpure bis(p-hydroxyphenyl)carbonate, m.p. 188°-189° C.; NMR (acetone-d₆):δ 7.00(q,8), 3.01(s,2); HPLC retention time of 6.89 minutes (μ-Porasilcolumn 4 mm. ID×30 cm. length, solvent 9.75% acetonitrile+90.25%ethylene dichloride); and the following elemental analysis

Calcd. for C₁₃ H₁₀ O₅ : C, 63.42%; H, 4.09% Found: C, 63.28%; H, 4.06%.

The monophenol or p-cumyl(p-hydroxyphenyl)carbonate was recrystallizedfrom either benzene or carbon tetrachloride, m.p. 126°-128° C.; infraredabsorption spectrum (cm⁻¹): 3580, 3420, 3015, 2978, 1755, 1580, 1495,1435, 1230, 1170, 1088, 1045, 1001, 878, 819; NMR (acetone-d₆): δ 7.13(m,4), 6.87 (q,4), 2.94 (m,1), 1.13 (d,6), 8.40 (s,1); HPLC retentiontime of 3.29 minutes (same conditions as above); and the followingelemental analysis

Calcd. for C₁₆ H₁₆ O₄ : C, 70.57%; H, 5.92% Found: C, 70.47%; H, 5.87%.

EXAMPLE 6

A round bottom flask equipped according to Example 1 was charged with14.90 g. (0.05 mole) of di(p-cumyl) carbonate, 0.03 g. (0.20 wt. %) ofcopper phthalocyanine, 0.15 g. (1.0 wt. %) of t-butyl hydroperoxide, and5 g. (33.6 wt. %) of chlorobenzene. Oxygen was bubbled into the solution(flow rate about 20 ml./min.) for 5 minutes at a solution temperature of125°-130° C. and thereafter for 2.75 hours at 115°±3° C. NMR showed thefollowing molar hydroperoxide formation: after 0.5 hour, 5.3%; 1.0 hour,9.5%; 1.5 hours, 16.3%; 2 hours, 24.3%; 2.5 hours, 31.8%; 2.75 hours,33.3%. The rate of conversion was 12 mole %/hour. There was no inductionperiod. HPLC showed the following selectivity.

(p-hydroperoxyisopropylphenyl)cumyl carbonate 85.7%

(p-hydroxyisopropylphenyl)cumyl carbonate 6.0%

di(p-hydroperoxyisopropylphenyl)carbonate 6.0%

(p-hydroxyphenyl)cumyl carbonate 1.5%.

EXAMPLE 7

A round bottom flask equipped according to Example 1 was charged with28.50 g. (0.16 mole) of m-isopropylphenyl acetate, 0.6 g. (0.21 wt. %)of copper phthalocyanine, and 0.30 g. (1.1 wt. %) of t-butylhydroperoxide. Oxygen was bubbled into the stirred solution (flow rate20 ml./min.) for 15 minutes at a solution temperature of 125°-130° C.and thereafter for 6.5 hours at 115°±3° C.

NMR monitoring showed the following molar hydroperoxide formation: after60 minutes, 3.63%; 120 minutes, 10.0%; 180 minutes, 13.1%; 270 minutes,20.5%, 360 minutes, 23.0%; finally at 390 minutes, 24.9%. The rate ofconversion was 4.8 mole %/hour. There was no induction period. HPLCanalysis showed the following selectivity.

m-hydroperoxyisopropylphenyl acetate 95.8%

m-acetoxyacetophenone 1.59%

m-hydroxyisopropylphenyl acetate 6.32%.

EXAMPLE 8

m-Isopropylphenol, 36.06 g. (0.265 mole) was dissolved in dilute excesssodium hydroxide solution. To this solution was added 1 g. oftriethylamine and during rapid stirring there was added dropwise asolution of 28.4 g. (0.14 mole) of terephthaloyl dichloride dissolved in150 ml. of methylene dichloride. The reaction solution was cooled untilthe addition was completed.

The organic layer was separated and the aqueous layer extracted with2×100 ml. of methylene chloride and combined with the organic layer. Thesolution was evaporated in vacuo and yielded 51.18 g. of product.Recrystallization from methanol yielded 51.01 g. (95.4%) ofdi(m-isopropylphenyl)terephthalate, m.p. 79°-81° C.; NMR (CDCl₃): δ 8.32(s,4), 6.90-7.40 (m,8), 2.98 (m,1), 1.31 (d,12).

Into a round bottom flask equipped according to Example 1 there wasadded 41.0 g. (0.10 mole of the di(m-isopropylphenyl)terephthalateprepared above, 0.4 g. (1 wt. %) of t-butyl hydroperoxide, 0.08 g. (0.2wt. %) of copper phthalocyanine, and 10 ml. of benzene. Oxygen wasbubbled into the solution (flow rate 20 ml./min.) at a temperature of115°±3° C. for 10 hours and 15 minutes. NMR analysis showed thatconversion to hydroperoxide was 11.6 mole % after 1 hours and 35 mole %when the reaction was stopped after 10 hours.

The hydroperoxide consisted of a mixture of predominantlym-isopropylphenyl-m-hydroperoxyisopropylphenyl terephthalate and thedi(m-hydroperoxyisopropylphenyl) terephthalate. No attempt was made toseparate the compounds.

EXAMPLE 9

The following process although not in accordance with the presentinvention was employed to obtain 3,5-di(hydroperoxyisopropyl)phenylbenzoate.

A round bottom flask equipped according to Example 1 was charged with9.1 g. (0.0322 mole) of 3,5-diisopropylphenyl benzoate, 0.09 g. (1.0 wt.%) of di-t-butyl peroxide, and 15 g. of chlorobenzene. Oxygen wasbubbled into the solution (flow rate about 15 ml./min.) for 10 minutesat a solution temperature of 120°-125° C. and thereafter for 7 hours at115° C. NMR showed the following molar hydroperoxide formation: after1.5 hours, 3%; 4 hours, 14.1%; 5 hours, 19.3%; and 7 hours, 23.3%. Thereaction temperature was reduced to 90°-95° C. and the reaction wasallowed to continue overnight at that temperature and at the oxygen flowset forth above.

After a 16 hour period at the 90°-95° C. temperature the percent molarhydroperoxide conversion was 36.7% and the reaction stopped at a 38.8%conversion.

HPLC showed the following selectivity distribution.

3-hydroperoxyisopropyl-5-isopropylphenyl benzoate 56.5%

3,5-di(hydroperoxyisopropyl)phenyl benzoate 37.2%

3-hydroxyisopropyl-5-isopropylphenyl benzoate 6.2%.

The rate of conversion was 4.6 mole %/hour measured over the reactionperiod from the second to the fifth hour.

The reaction product mixture was stirred with 75 ml. of pet ether whichcaused the precipitation of 2.14 g. of crystalline residue; m.p.105°-108° and consisted of 60% by weight of the dihydroperoxy productand 40% of the monohydroperoxide. Recrystallization of the precipitatefrom chloroform provided the pure 3,5-di(hydroperoxyisopropyl) phenylbenzoate; m.p. 122°-124° C., NMR (CDCl₃): δ 8.48 (s,2), 8.16 (m,2), 7.45(m,4), 7.16 (d,2), 1.62 (s,12); and the following elemental analysis

Calcd. for C₁₉ H₂₂ O₆ : C, 65.88%; H, 6.40% Found: C, 65.68%; H, 6.51%.

A 0.62 g. sample of the dihydroperoxide product was rearranged in 10 ml.of benzene with 2 drops of boron trifluoride etherate at 60° C. Thereaction was instantaneous with the immediate formation of thecrystalline 3,5-dihydroxyphenyl benzoate, 0.31 g. (75% yield), m.p.195°-196° C.

Shaking the dihydroxyphenyl benzoate in dilute aqueous caustic solutionprovides 1,3,5-trihydroxybenzene (phloroglucinol).

EXAMPLE 10

Using the procedure and ingredients set forth in Example 5 for thepreparation of bis(p-isopropylphenyl) carbonate except that thep-isopropylphenol was replaced by an equivalent amount of3,5-diisopropylphenol, there was preparedbis(3,5-diisopropylphenyl)carbonate in a crude yield of 100%.Recrystallization of the product from methanol provided a 77.8% pureyield; m.p. 53°-55° C.; infrared absorption spectrum (CHCl₃) (cm⁻¹)2965, 2930, 2875, 1780, 1615, 1591, 1468, 1460, 1442, 1226, 1160, 1127,1000, 940, and 670; NMR (CCl₄) at δ 6.92 (s, 6), δ 2.91 (m,4), δ 1.30(d,24); elemental analysis,

Calcd. for C₂₅ H₃₄ O₃ : C, 78.49%; H, 8.96% Found: C, 78.26%; H, 8.91%.

The following process although not in accordance with the presentinvention was employed to obtainbis(3,5-dihydroperoxyisopropylphenyl)carbonate.

A round bottom flask equipped according to Example 1 was charged with19.1 g. (0.05 mole) of the bis(3,5-diisopropylphenyl)carbonate preparedabove, 0.20 g. (1 wt.%) of t-butyl hydroperoxide and 20 g.(approximately 100% w/w) of chlorobenzene. Oxygen was bubbled into thesolution (flow rate about 15 ml./min.) at a solution temperature of115°±3° C. and the progress of the autoxidation monitored by NMR. After3 hours the percent molar conversion was 8.1%; 5 hours, 17.5%; and 6.25hours, 25%. The reaction was continued overnight (for a 14 hour period)at 100° C. The final conversion was 62.7%. HPLC analysis showed thepresence of five major hydroperoxide products.

The reaction solution was diluted with 150 ml. of chlorobenzene andafter standing overnight, 0.75 g. of precipitatedbis(3,5-dihydroperoxyisopropylphenyl)carbonate was collected, m.p.119°-130° C. Recrystallization from chloroform provided pure material,m.p. 135°-138° C., elemental analysis,

Calcd. for C₂₅ H₃₄ O₁₁ : C, 58.81%; H, 6.71% Found: C, 57.89%; H, 6.98%.

The remaining chlorobenzene solution was treated with 6 drops (about 0.1g.) of boron trifluoride etherate at a temperature of 30°-40° C. Anexothermic reaction ensued and the temperature was controlled to a rangeof 50°-80° C. by a water bath over a 2 hour period during stirring.

The reaction solution was added to 100 ml. of ether and this solutionshaken with 3×25 ml. portions of 15 percent aqueous sodium hydroxide.The ether layer upon evaporation yielded 4.06 g. of starting carbonatematerial. The aqueous layer was acidified and extracted with ether. HPLCanalysis revealed two major components corresponding to3,5-dihydroxyisopropylbenzene (R_(T) =3.75 minutes) and1,3,5-trihydroxybenzene (R_(T) =9.40 minutes) on a μ-Porasil column (4mm. ID×30 cm. length) operating at a flow rate of 1.5 ml./min. in asolvent mixture of 16% by wt. acetonitrile in ethylene dichloride.

The two products were separated by column chromatography using a drypacked silica gel column eluted with ether. When 3.50 g. of the mixturewas diluted in 10 ml. of ether and eluted through a 2 cm.×40 cm. columnthere was obtained as separated products 1.52 g. of the3,5-dihydroxyisopropylbenzene, 0.49 g. of 1,3,5-trihydroxybenzene, and0.31 g. of unidentified material.

EXAMPLE 11

A round bottomed flask equipped according to Example 1 was charged with17.8 g. (0.1 mole) of p-isopropylphenyl acetate, 0.09 g. (0.5 wt. %) oft-butyl hydroperoxide, and 0.15 g. of di-t-butyl peroxide (0.8 wt. %).Oxygen was bubbled into the solution (flow rate 8-10 ml./min.) at asolution temperature of 115°±3° C. The temperature control apparatusallowed the initial temperature to rise to about 120° C. for a fewminutes prior to settling on the controlled value. The mole percentconversion was determined by NMR and product selectivity by HPLC. At theend of a 4 hour reaction period the mole % conversion was 22.5% at aconversion rate of 5.62 mole % per hour with no induction period. Theproduct distribution was found to be: 96.9% p-hydroperoxyisopropylphenylacetate, and 3.1% p-hydroxyisopropylphenyl acetate.

EXAMPLE 12

A round bottomed flask equipped according to Example 1 was charged with17.8 g. (0.1 mole) of p-isopropylphenyl acetate, 0.27 g. (1.5 wt. %) ofdicumyl peroxide, 0.153 g. (0.86 wt. %) of cumyl hydroperoxide, and 6 g.of chlorobenzene. Oxygen was bubbled into the solution (flow rate 10ml./min.) at a solution temperature of 115°±3° C. (See Example 11 forexplanation of an initial temperature rise to 120° C.). At the end of a5 hour reaction period the mole % conversion was 33.3% at a rate of 7.48mole % per hour with no induction period. The selectivity was found tobe: 93.4% p-hydroperoxyisopropylphenyl acetate, and 6.6%p-hydroxyisopropylphenyl acetate.

EXAMPLE 13

A round bottomed flask equipped according to Example 1 was charged with17.8 g. (0.1 mole) of p-isopropylphenyl acetate, 0.27 g. (1.5 wt. %) ofdicumyl peroxide, 0.10 g. (0.56 wt. %) of t-butyl hydroperoxide, and 6.0g. of chlorobenzene. Oxygen was bubbled into the solution (flow rate 10ml./min.) at a solution temperature of 115°±3° C. (See Example 11 forexplanation of an initial temperature rise to 120° C.). At the end of a3.5 hour reaction period the mole % conversion was 32.7% at a rate of10.1 mole % per hour with no induction period. The selectivity was foundto be: 93.5% p-hydroperoxyisopropylphenyl acetate, and 6.5%p-hydroxyisopropylphenyl acetate.

EXAMPLE 14

A round bottomed flask equipped according to Example 1 was charged with17.8 g. (0.1 mole) of p-isopropylphenyl acetate, 0.15 g. (0.84 wt. %) ofdi-t-butyl peroxide, 0.15 g. (0.84 wt. %) of cumyl hydroperoxide, and6.0 g. of chlorobenzene. Oxygen was bubbled into the solution (flow rate10 ml./min.) at a solution temperature of 115°±3° C. (See Example 11 forexplanation of an initial temperature rise to 120° C.). At the end of a6.0 hour reaction period the mole % conversion was 28.7% at a rate of5.26 mole % per hour with no induction period. The selectivity was foundto be: 95.8% p-hydroperoxyisopropylphenyl acetate, and 4.2%p-hydroxyisopropylphenyl acetate.

EXAMPLE 15

The following experiment not in accordance with the present inventionillustrates how a low temperature free radical initiating reagent likeazo-bis-isobutyronitrile will not give the same high conversions withhigh product selectivity as does the present invention.

A round bottomed flask equipped according to Example 1 was charged with17.8 g. (0.1 mole) of p-isopropylphenyl acetate, 0.10 g. (0.56 wt. %) oft-butyl hydroperoxide, 0.17 g. (0.96 wt. %) of azo-bis-isobutyronitrile,and 9 g. of chlorobenzene. Oxygen was bubbled into the solution (flowrate 10 ml./min.) at a solution temperature of 85°±3° C. After 1.5 hoursof reaction the NMR analysis showed the complete disappearance of theazo-bis-isobutyronitrile and substantial decomposition of hydroperoxide.After a 2 hour reaction period the mole % conversion was 19.8% at a rateof 9.90 mole % per hour. The selectivity was found to be low for desiredproduct at 78.6% p-hydroperoxyisopropylphenyl acetate, 16.1%p-hydroxyisopropylphenyl acetate, and 5.3% p-acetoxyacetophenone.

Repetition of the autoxidation at a lower temperature (70°±3° C.) in anendeavour to lower hydroperoxide decomposition lead to an observedincrease of product selectivity of 89.1%. However, the rate over a 4hour reaction period was only 3.18 mole % per hour and the mole %conversion was only 12.7%.

EXAMPLE 16

The following experiment not in accordance with the present inventionillustrates how when only one of the catalyst components is employed butat a higher concentration which is approximately equal to the sum totalfor the two catalysts in accordance with the invention that the rate ofthe reaction is lowered and a long induction period results.

A round bottomed flask equipped according to Example 1 was charged with17.8 g. (0.1 mole) of p-isopropylphenyl acetate and 0.36 g. (2 wt. %but, more importantly, when calculated on a mole % basis it is 2.47 mole% which is more than twice as much as the concentrations used incomparative examples) of di-t-butyl peroxide. Oxygen was bubbled intothe solution (flow rate 10 ml./min.) at a solution temperature of115°±3° C. After a 6.5 hour reaction period the mole % conversion was23.0 mole % at a rate of only 3.73 mole % per hour. There was aninduction period of about 1 hour before inception of the autoxidation.The selectivity was found to be: 94.5% p-hydroperoxyisopropylphenylacetate and 5.5% p-hydroxyisopropylphenyl acetate.

EXAMPLE 17

The following experiments not in accordance with the present inventionillustrate how three known autoxidizing agents will not give the samehigh conversion rates or induction free reactions in accordance with thepresent invention.

A round bottomed flask equipped according to Example 1 was charged with17.8 g. (0.1 mole) of p-isopropylphenyl acetate, and 0.15 g. (0.84 wt.%) of cumyl hydroperoxide. Oxygen was bubbled into the solution (flowrate 8-10 ml./min.) at a solution temperature of 115°±3° C. After an 8.0hour reaction period the mole % conversion was only 20.2% at a rate ofonly 2.53 mole % per hour. There was almost a 2 hour induction periodbefore the autoxidation began. The selectivity was 96.8%p-hydroperoxyisopropylphenyl acetate and 3.2% p-hydroxyisopropylphenylacetate.

The experiment was repeated using t-butyl hydroperoxide in the sameconcentration. After a 7 hour reaction period the conversion was only 13mole % at a rate of 1.86 mole % per hour with an induction period justslightly over 1.5 hours. The selectivity was 97.7%p-hydroperoxyisopropylphenyl acetate and 2.3% p-hydroxyisopropylphenylacetate.

When the same autoxidation was performed using 30% hydrogen peroxide inthe same concentration after 7 hours the conversion was only 2.6 mole %at the rate of 0.37 mole % per hour and with a 3.75 hour inductionperiod. Selectivity was not determined.

I claim:
 1. A dihydroperoxide having the formula ##STR6##
 2. Atetrahydroperoxide having the formula ##STR7##